Alcohols derived from babassu oil



United States Patent No Drawing. Application December 2, 1953 Serial No.395,836 3 Claims. (Cl. 260-632) This invention pertains to a novelcomposition of matter and the production thereof, and in particular isconcerned with the production of a novel mixture of alcohols derivedfrom babassu oil.

Babassu kernel oil is obtained from the kernels of the seed or nut of avariety of palm. The oil is generally obtained by first decorticatingthe seed or nut to remove the shell from the kernel and the kernel isthen subjected to either an expression or extraction operation in orderto obtain the oil. Normally, the oil is not subjected to furthertretament except perhaps washing, deacidification, or the like. The oilsthus obtained have been used primarily in the soap and edible fatindustries. As a result of my work in this field, I have found that anovel composition can be obtained from babassu oil which has manyadditional and diverse uses other than the uses employed for the oilitself thus far.

It is an object therefore of this invention to provide a new and novelcomposition of matter. A further object is to provide a mixture ofalcohols derived from babassu oil. A still further object of thisinvention is to provide a process for preparing this mixture ofalcohols. Other objects of this invention will become apparent from thediscussion hereinafter.

The novel composition of this invention is a mixture of alcoholscorresponding in the number of carbon atoms to the fatty acid radicalsof babassu oil. The novel composition of this invention is obtained whenbabassu oil is reduced by an alkali metal-reducing alcohol process. Themixture of alcohols is characterized in that the unsaturation of theoriginal babassu oil is retained when using an alkali metal-alcoholreduction process. Thus, this invention provides a novel mixture ofalcohols having properties for various uses as further described hereinafter.

The raw material from which the novel composition of this invention isobtained will vary somewhat in analysis. It is to be understood that themixture of alcohols of this invention includes the mixture obtained by areduction process when treating the raw oil and also oil which has beenrefined in various ways such as, for example, deacidification and thelike. A typical analysis of babassu oil is as follows:

Unsaturated fatty acid constituents percent 13 Oleic-l2.2 percentLino1eicl.l percent Saturated fatty acid constituents ..percent 87Caproic0.3 percent Caprylic--7.l percent Capric8.3 percent Laurie-47.3percent Myristic14.5 percent Palmitic-7.l percent Stearic-2.0 percentArachidic0.1 percent Saponification number 254.1 Acid number 6.8 Esternumber 247.3 Iodine number 19.3

Babassu oil comprises primarily triglycerides of the fatty acids.Therefore, the fatty acid constituent percentages above are percentagesof the total fatty acid portion of the triglycerides. The fatty acidportion of the triglyceride comprises fatty acids containing 6 to 20carbon atoms both saturated and unsaturated.

The novel composition of this invention is the mixture of alcoholsobtained when reducing a raw mate rial such as typified above. Themixture of alcohols will vary corresponding to the variance in analysisof the starting material. However, the analysis of this new and novelcomposition will comprise at least a weight percent hydroxyl of 6.0,Wijs iodine number of at least 18.0, an acid number not greater than5.0, and a saponification number not greater than 10.0. The number ofcarbon atoms of the individual alcohols of the mixture will correspondto the number of carbon atoms of the fatty acids of the startingmaterial with very little, if any, change in unsaturation. Becauseof thevariance in analysis of the starting material, the average molecu- "larweight of the novel mixture of alcohols of this invention cannot bedefined precisely. However, the average molecular weight ordinarily willbe greater than and generally between about and 210.

As mentioned above, the novel composition of this invention is producedby treating babassu oil simultaneously with an alkali metal and areducing alcohol. Briefly, the process involves reacting the fatty acidesters with an alkali metal and a reducing alcohol, hydrolyzing thealkali metal alcoholates thus formed, and separating the high molecularweight alcohols from the re ducing alcohol, caustic, solvent, andglycerol, when the triglycerides are reduced. In a typical process, butby no means limiting, between about the stoichiometric equivalent amountand 5 percent excess of the alkali metal is employed over that requiredto produce the corresponding alcoholates. Similarly, between about thestoichiometric equivalent amount and 5 percent excess of a reducingalcohol is employed over the theoretical requirement. The alcoholatesformed are hydrolyzed by treating with water and the product alcoholsare separated therefrom. The chemical reactions involved can be depictedas follows:

CHr-OH where R, R and R can be the same or different and are carbonchains having about 6 to 20 carbon atoms, R is an alkyl radical, and Mis an alkali metal.

In carrying out the above reactions to prepare the alcohol mixture ofthis invention, a preferred method is to utilize the alkali metal in theform of subdivided particles. Alkali metal dispersions which are wellknown in the art, are well suited for this purpose. These dispersionsare prepared by melting the alkali metal in an inert organic mediumwhich generally has a boiling point above the melting point of thealkali metal. During this operation the mixture is highly agitated inorder to form the dispersion. Various dispersion media are well known inthe art and can be employed in preparing the alkali metal dispersions.Among such media are for example, toluene, xylene, dihydronaphthalene,petroleum fractions, heavy alkylates, and the like. Still otherdispersion media can be employed, the foregoing serving merely asillustrative examples. The proportion of the alkali metal to thedispersion medium can be varied, and dispersions having metalconcentrations from about trace quantities to about 60 percent by weightare common. It is preferred to utilize about a 50 percent by weight, orless, dispersion. Likewise, the particle size will vary and the solutionwill have particles averaging about 50 microns in size and smaller. Itis preferred that the particle size average less than about 20 microns.Smaller particle sizes enhance the reaction rate and provide increasedcontact between the metal and the babassu oil and reducing alcohol.Although any of the alkali metals can be employed, sodium is preferredhere, primarily because of its greater availability and economy.

The reducing alcohols employed when producing the composition of thisinvention can be the primary, secondary, or tertiary alcohols. Forexample, lower molecular Weight primary, secondary, or tertiaryalcohols, such as those having less than about 10 carbon atoms can beused. Likewise, the alcohols produced by the process can be employed asreducing alcohols, and these include alcohols having from about 10 to 30carbon atoms. However, it is preferred to utilize the secondary alcoholsinasmuch as it has been found that they are less reactive toward thealkali metal and are quite suitable for use in ester reductionprocesses. Among such secondary alcohols are for example, propanol-Z,butanol-2, pentanol-Z, pentanol-3, methylisobutylcarbinol,2-methylbutanol-3, hexenol-Z, hexanol-3, phenylmethyl carbinol,phenylethyl carbinol, cyclopentanol, and cyclohexanol. Still othersecondary alcohols can be employed, the foregoing serving merely asillustrative examples.

The solvent used in this process can be any solvent which is unreactivewith the particular reactants of the process. In a preferred embodiment,the solvent which is employed is the same organic material utilized inthe preparation of the alkali metal dispersion. However, other materialscan be used to equal advantage. The proportion of the solvent employedcan vary within wide limits. The proportion of solvent to ester can bebetween the limits of 0.25 and 5.0 to l, and, preferably, between 0.25and 1.3 to 1 part by weight.

To further demonstrate the novel composition of this invention and aprocess for its manufacture, reference is made to the following examplewherein all parts and percentages are by weight.

To a vessel equipped with external heating, a hold-up tank, and a meansfor agitation was added 85.8 parts of sodium and 173 parts of toluene.This mixture was then vigorously agitated and heated to a temperature ofabout 110 C. thereby producing a dispersion of sodium. To thisdispersion was added a mixture of 200 parts babassu oil (saponificationnumber, 254.1; acid number, 6.8; iodine number, 19.3; percent hydroxyl,173 parts of toluene, and 198 parts of methylisobutylcarbinoi over aperiod of 45 minutes. The mixture was maintained at the refluxtemperature during this period about 173 parts of toluene were removedtherefrom by vaporization and hold-up. When the addition was completed,the mixture was permitted to reflux for an additional 15 minutes. At theend of this period, the reduction mixture was mixed with 746 parts ofhot water in order to hydrolyze the alcoholates formed. During thehydrolysis, 15 parts of water and 52 parts of toluene were removed byvaporization in order to break a slight emulsion which had formed. Thehydrolyzed mixture then separated into 2 layers and the water layercontaining caustic and glycerine was removed therefrom. The organiclayer was washed with additional water to result in a solution having apH of about 7.0. The thus washed organic layer was then distilled underreduced pressure to remove the toluene and methylisobutylcarbinol. Themixture of product alcohols, representing a yield of 87 percent, had asaponification number of 5.8; acid number of 2.8; iodine number of 21.5;and a percent hydroxyl of 8.2.

The novel composition of this invention can be prepared by similarmethods of ester reduction other than the particular mode or sequence ofoperations described in the preceding example. It is to be understoodthat the specific proportions disclosed here are merely illustrative andcan be varied within wide limits. Similarly, lay-products such asglycerine and caustic can be recovered for their values. Ordinarily thesolvent and reducing alcohol will be recycled for reuse in the process.

Other variations in the over-all ester reduction process can be made. Ithas been found that the raw babassu oil can be first transesterified,preferably with an alcohol corresponding to the reducing alcohol. Apreferred method of transesterifying the glycerides is to react themwith an aliphatic alcohol in the presence of an alkaline alcoholysiscatalyst. In this manner, the glycerine is separated prior to the actualester reduction operation and is replaced by the esterifying alcohol. Inthis instance, a secondary alcohol is again preferred, such as, forexample, methylisobutylcarbinol and the like. The newly formed estersare then reduced similar to the process as indicated above. The chemicalreactions are essentially the same with exception that monoesters willbe reduced rather than triglycerides and the proportion of reactantswill vary accordingly. A particular advantage of this technique is thatglycerine yield is greater.

The novel composition of this invention can be applied to a variety ofuses. When the mixture of alcohols is sulfated or sulfonated, improvedalkyl sulfate and sulfonate detergents, wetting agents, emulsifiers, andthe like are produced. In some instances, the sulfating or sulfonatingagent may react with some of the unsaturated portions of the mixture.Likewise, various sulfation techniques can be employed which selectivelysulfate only the hydroxyl radical of the alcohols of this invention. Thesalts of these products can be formulated with other sulfonatedproducts, such as dodecylbenzene sulfonic acid, with amides, inorganicphosphates, and sulfates, and the like constituents of syntheticdetergent compositions.

A still further use for the novel composition of this inventioncomprises additives and additive intermediates for lubricants. Thus, forexample, when the mixture of alcohols of this invention or theirderivatives such as, for example, esters, metal salts, and the like, isadded to mineral lubricating oils, it will enhance their lubricantproperties. Likewise, when the sulfated and sulfonated derivatives, asmentioned above, of the mixture of alcohols are employed in thelubricating oils, improved lubricants are obtained.

The novel mixture of alcohols of this invention is also admirably suitedas an intermediate for the production of other useful organic chemicalsor mixtures thereof. For example, the double bonds of the unsaturatedconstituents can be subjected to any of the known reactions of doublebonds to produce compounds such as epoxides, halogenation derivatives,and the like. Further, the alcohols can be reacted with various acids toproduce the corresponding esters. Likewise, they may be oxidized toproduce the corresponding aldehydes and acids. A still further use ofthe novel composition of this invention is that it, and its ester andether derivatives can be employed as a plasticizer composition.Additionally, when the novel mixture of alcohols of this invention isfractionated, as for example, into a fraction containing lower molecularweight alcohols and a fraction containing the higher alcohols, thesefractions can be employed in the foregoing uses and others. These andmany other uses will be apparent to those skilled in the art.

Having thus described the novel composition of this invention and aprocess for its manufacture, it is not intended that it be limitedexcept as noted and prescribed in the following claims.

I claim:

1. As a new composition of matter, a mixture essentially of highermolecular alcohols derived from babassu oil corresponding in the numberof carbon atoms, degree of unsaturation, and in substantially the samepercentages to the fatty acid radicals of said oil, said mixture beingcharacterized by having an average molecular weight greater than 160, apercent hydroxyl of at least 6.0, and an iodine number of at least 8.0.

2. As a new composition of matter a mixture essentially of highermolecular alcohols derived from babassu oil, said alcohols correspondingin the number of carbon atoms and degree of unsaturation to, and insubstantially the same percentages as, the fatty acid radicals ofbabassu oil, said mixture having a saponification number of about 5.8,an acid number of about 2.8, an iodine number of about 21.5, and percenthydroxyl of about 8.2.

3. A process for the manufacture of a mixture of alcohols derived frombabassu oil comprising reacting said oil with between about thestoichiometric equivalent amount and 5 percent in excess of that amountof sodium, and between about the stoichiometric equivalent amount and 5percent in excess of reducing alcohol in the presence of between 0.25 to5 parts by weight of an inert organic solvent based upon the weight ofsaid oil, hydrolyzing the resulting mixture, and separating the productalcohols from the reducing alcohol and solvent thereby recovering amixture of higher molecular alcohols corresponding in the number ofcarbon atoms to the fatty acid radicals contained in babassu oil withessentially the same degree of unsaturation and in substantially thesame percentages as the fatty acid radical of said oil.

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1. AS A NEW COMPOSITION OF MATTER, A MIXTURE ESSENTIALLY OF HIGHER MOLECULAR ALCOHOLS DERIVED FROM BABASSU OIL CORRESPONDING IN THE NUMBER OF CARBON ATOMS, DEGREE OF UNSATURATIOON, AND IN SUBSTANTIALLY THE SAME PERCENTAGES TO THE FATTY ACID RADICALS OF SAID OIL, SAID MIXTURE BEING CHARACTERIZED BY HAVING AN AVERAGE MOLECULAR WEIGHT GREATER THAN 160, A PERCENT HYDROXYL OF AT LEAST 6.0, AND AN IODINE NUMBER OF AT LEAST 8.0. 